Gelled biocidal treatments

ABSTRACT

A biocidal composition and method for inhibiting and controlling the growth of microorganisms are disclosed. The composition comprises an amount, effective for the intended purpose, of polyethylene glycols and bis(trichloro methyl) sulfone, in combination with additional biocidal components, the composition in a gel form. The method comprises administering an amount of the gelled composition to the particular water containing system for which treatment is desired.

BACKGROUND OF THE INVENTION

The formation of slimes by microorganisms is a problem that is encountered in many aqueous systems. For example, the problem is not only found in natural waters such as lagoons, lakes, ponds, etc., and confined waters as in pools, but also in such industrial systems as cooling water systems, air washer systems and pulp and paper mill systems. All possess conditions which are conducive to the growth and reproduction of slime-forming microorganisms. In both once-through and recirculating cooling systems, for example, which employ large quantities of water as a cooling medium, the formation of slime by microorganisms is an extensive and constant problem.

Airborne organisms are readily entrained in the water from cooling towers and find this warm medium an ideal environment for growth and multiplication. Aerobic and heliotropic organisms flourish on the tower proper, while other organisms colonize and grow in such areas as the tower sump and the piping and passages of the cooling system. The slime formation not only aids in the deterioration of the tower structure in the case of wooden towers, but also, by its deposition on metal surfaces, promotes corrosion. In addition, slime carried through the cooling system plugs and fouls lines, valves, strainers, etc., and deposits on heat exchange surfaces. In the latter case, the impedance of heat transfer can greatly reduce the efficiency of the cooling system.

In pulp and paper mill systems, slime formed by microorganisms is commonly encountered and causes fouling, plugging, or corrosion thereof. The slime also becomes entrained in the paper produced to cause breakouts on the paper machines, with consequent work stoppages and the loss of production time, and/or is responsible for unsightly blemishes in the final product, which result in rejects and wasted output.

The previously discussed problems have resulted in the extensive utilization of biocides in cooling water and pulp and paper mill systems. Materials which have enjoyed widespread use in such applications include chlorine, chlorinated phenols, organo-bromines, and various organo-sulfur compounds. All of these compounds are generally useful for this purpose but each is attended by a variety of impediments. For example, chlorination is limited both by its specific toxicity for slime-forming organisms at economic levels and by the tendency of chlorine to react, which results in the expenditure of the chlorine before its full biocidal function is achieved. Other biocides are attended by odor problems and hazards in respect to storage, use or handling which limit their utility. To date, no one compound or type of compound has achieved a clearly established predominance in respect to the applications discussed. Likewise, lagoons, ponds, lakes, and even pools, either used for pleasure purposes or for industrial purposes for the disposal and storage of industrial wastes, become, during the warm weather, besieged by slime due to microorganism growth and reproduction. In the case of recreational areas, the problem of infection is obvious. In the case of industrial storage or disposal of industrial materials, the microorganisms cause additional problems which must be eliminated prior to the materials' use or disposal of the waste.

Naturally, economy is a major consideration in respect to all of these biocides. Such economic considerations attach to both the cost of the biocide and the expense of its application. The cost performance index of any biocide is derived from the basic cost of the material, its effectiveness per unit of weight, the duration of its biocidal or biostatic effect in the system treated, and the ease and frequency of its addition to the system treated. To date, none of the commercially available biocides has exhibited a prolonged biocidal effect. Instead, their effectiveness is rapidly reduced as a result of exposure to physical conditions such as temperature, association with ingredients contained by the system toward which they exhibit an affinity or substantivity, etc., with a resultant restriction or elimination of their biocidal effectiveness, or by dilution.

In addition, the majority of the previously discussed biocides are liquid, organic solvent-based formulations, which may pose environmental, health and safety concerns. With increasing public awareness and governmental legislation related to chemical spills, environmental hazards, and health and safety in the workplace, improved methods of formulating, packaging and handling biocides are of growing interest.

SUMMARY OF THE INVENTION

The biocidal compositions of the present invention comprise gelled mixtures of polyethylene glycols, bis (trichloro methyl) sulfone, a quaternary ammonium halide salt and an alkylphenol ethoxylate.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides an improvement over previous biocide formulations and applications techniques. It has been discovered that biocides may be formulated as water and/or polymer-based products which are gels at ambient (less than 120° F.) temperatures. The gelled biocides are essentially in a plastic, semi-solid or waxy form, and can be supplied as a bulk gel in buckets or drums, in molded form (gel logs or briquettes), or as a bulk solid (gel beads or flakes). The advantages of gelled biocides are reduced spill hazards, reduced odor, fire and explosion hazards, and improved handling and worker safety. The elimination of organic solvents provides both an economic and health and safety advantage.

The following example illustrates the feasibility of gelled biocide technology. In addition, many other formulations and applications are possible which would be obvious to those skilled in the art, and all such modifications should be considered within the scope and spirit of this invention.

    ______________________________________                                         I. Sulfone/Polyethylene glycol (PEG)                                                               Approximate Weight                                                             Percentages                                                ______________________________________                                         Polyethylene glycol   58%                                                      Bis (trichloro methyl) sulfone (sulfone)                                                             20%                                                      Quaternary alkyldimethylbenzyl                                                                       19%                                                      ammonium chloride (quat)                                                       Nonylphenol ethoxylate                                                                                3%                                                      ______________________________________                                    

Experiments were conducted using polyethylene glycols (PEG) and blends of polyethylene glycols (400-2000 mw) which are solid at room temperature, and have melting points of about 100°-150° F. It was found that certain biocides, e.g., sulfone/quat, were soluble in molten PEG. On cooling, the PEG/biocide formed a solid with a distinct melting point. The solid is also somewhat soluble in water. The molten solution is transferred to containers (drums, buckets, molds, etc.) and allowed to solidify or gel.

The following weight ranges of particular components are anticipated to be effective: 50-90% PEG, 3-30% sulfone, 3-30% quat and 1-5% nonylphenol ethoxylate.

In accordance with the present invention, the gelled biocidal treatment may be added to the desired aqueous system in need of biocidal treatment, in an amount of from about 0.1 to about 200 parts of the treatment to one million parts (by weight) of the aqueous medium. Preferably, about 5 to about 50 parts of the treatment per one million parts (by weight) of the aqueous medium is added.

The method of preparing the gelled PEG biocide is as follows: The PEG is first melted in a heated vessel with an overhead stirrer. The liquid sulfone and remaining ingredients are then added and blended until the mixture is uniform. The mixture is then poured into drums, molds, etc., and allowed to cool. The gel is thermally reversible once it is formed, with a melting point of from about 100°-200° F.

The gelled biocide is added to a system by melting and feeding the preparation as a hot liquid. This feeding may be by means of adding gel logs, briquettes, etc., to the system and allowing them to dissolve. Alternatively, a process slip-stream may be passed across the gelled biocide and then returned to the system.

While we have shown and described herein certain embodiments of the present invention, it is intended that there be covered as well any change or modification therein which may be made without departing from the spirit and scope of the invention. 

We claim:
 1. A method for controlling the growth of microorganisms in an aqueous system which comprises adding to said system a gelled biocidal composition, said composition comprising a polyethylene glycol, bis(trichloro methyl) sulfone, a quaternary ammonium halide salt and an alkylphenol ethoxylate.
 2. The method as recited in claim 1 wherein said composition is added to said system in an amount of from about 0.1 to about 200 parts per million of said aqueous system.
 3. The method as recited in claim 1 wherein said gelled biocidal composition is in a plastic, semi-solid or waxy form.
 4. The method as recited in claim 1 wherein said gelled biocidal composition is in a molded form or a bulk solid.
 5. The method as recited in claim 1 wherein said aqueous system comprises a cooling water system.
 6. The method as recited in claim 1 wherein said aqueous system comprises a pulping and papermaking system.
 7. The method as recited in claim 1 wherein said quaternary ammonium halide salt is a quaternary alkyldimethylbenzyl ammonium chloride.
 8. The method as recited in claim 1 wherein said gelled biocidal composition is thermally reversible, with a melting point of from about 100°-200° F.
 9. A method for controlling the growth of microorganisms in an aqueous system which comprises adding to said system a gelled biocidal composition, said composition comprising about 50-90 weight percent of a polyethylene glycol, about 3-30 weight percent of bis(trichloro methyl) sulfone, about 3-30 weight percent of a quaternary ammonium halide salt and about 1-5 weight percent of an alkylphenol ethoxylate. 